Polymeric triazole compositions useful as cold drawn fibers or shaped articles



United States Patent POLYMERIC TRIAZOLE COMPOSITIONS USEFUL AS COLDDRAWN FIBERS OR SHAPED ARTICLES Gaetano F. DAlelio, Pittsburgh, Pa.,assignor to Koppers Company, Inc., a corporation of Delaware No Drawing.Continuation of application Serial No. 244,697, August 31, 1951. Thisapplication June 26, 1953, Serial No. 364,506

15 Claims. (Cl. 260--80.5)

This invention relates to new monomers and to new polymeric materialsderived therefrom and is particularly directed to the polymerizationproducts obtained by polymerizing a mass comprising as a new monomer anamide of acrylic or methacrylic acid and a diamino- 1,2,4-triazole inthe presence or absence of other ethylenic copolymerizable compoundsespecially acrylonitrile. The invention also relates to compositions ofthese polymerization products adapted to the formation of shapedarticles, in many cases to molecularly oriented shaped articles,particularly to fibers, threads, bristles, monofilarnents, etc.,hereinafter referred to as fibers, and other shaped articles such asfilms and' the like, which articles show improved dyeing properties.

It has been known for some time that certain copolymers of acrylonitrilemay be adapted to the preparation of shaped articles, such as, films,fibers, foils, tubes, etc. Some of these copolymers have been regardedas capable of being cold-drawn to produce structures molecularlyoriented along the fiber axis. Cold-drawing may be defined as thestretching of a polymeric material at a temperature below the meltingpoint of the material to give a molecularly oriented structure.

The resistance of acrylonitrile polymers to dyes of all types haspresented serious dyeing problems, especially in the development ofsynthetic fibers from these polymers. In fact, in order to dyepolyacrylonitrile one com mercial process resorts to the use of highpressures with water solutions or organic dispersions of dyes. It hasbeen proposed that improvement in dye susceptibility can be obtained bythe use of itaconic acid in small amounts as copolymerizing monomer inthe preparation of acrylonitrile polymers. However, the polymer productsobtained thereby have a tendency to crosslink upon standing attemperatures of at least about 7080 C. or upon spinning from hotsolutions. Such crosslinking causes spoliation of material by gelationduring storage, embrittlement of fibers, fouling of spinning jets, andother production difiiculties.

In accordance with the present invention it has now been found thatimprovements in dyeing properties of acrylonitrile polymers are obtainedby the polymerization of polymerizable masses comprising acrylonitrileand an amide of acrylic or methacrylic acid and adiaamino-l,2,4-triazole with or without other copolymerizable ethyleniccompounds. It has been found further that in addition to the fact thatamides of acrylic or methacrylic acid and diamino-1,2,4-triazoles yieldparticularly valuable copolymers with acrylonitrile, they may also beused effectively to form copolymers with other types of copolymerizableethylenic compounds. It has been found still further that the amides ofacrylic or methacrylic acid and diarnino-1,2,4-triazoles can bepolymerized per se to form useful polymers. Thus it has been found thatvaluable polymerization products may be prepared in accordance with theinvention by polymerizing a mass comprising an amide of acrylic ormethacrylic acid and a diamino-1,2,4-triazole either in the 2,859,485Patented Sept. 2, 1358 compounds such as acrylonitrile and the othercopolymerizable ethylenic compounds listed hereinafter.

The amides of acrylic or methacrylic acid and a diamino-l,2,4-triazoleare prepared readily by acylating guanazole (3,5-diamino-1,2,4-triazole)or a guanazole derivative with acrylic or methacryl acid or theanhydride or acid chloride of these acids. As guanazole is adifunctional base, both the monoand the diacyl derivative can be readilyprepared but the latter is advantageously avoided except wherecrosslinking is not objectionable. Preferably therefore the acylation iscarried out only to the mono stage. If desired one of the basic aminogroups may be acylated with some other acyl group such as formyl oracetyl or like alkanoyl group. For example, the mono-guanazolide ofacrylic acid (monoacrylguanazolide) forms readily when guanazole istreated with an equimolar proportion of acryl chloride or acrylicanhydride. Similarly, the mono-guanazolide of methacrylic acid(mono-methacrylguanazolide) is formed from guanazole and methacrylchloride or methacrylic anhydride. The acid chloride and anhydride aresuificiently reactive to form the amide merely upon mixing at roomtemperature. In some cases where the anhydride or acid chloride are notas reactive or in order to get more complete reaction gentle heating maybe advantageous. Guanazole is readily prepared by refluxing an aqueoussolution of dicyandiamide and a hydrazine salt, such as, thehydrochloride, and then neutralizing the acid. Otherdiamino-l,2,4-triazoles (substituted guanazoles) may be prepared inwhich one or more of the hydrogens are replaced by alkyl, aryl, aralkyl,alkaryl, and cycloaliphatic groups or in which one of the hydrogens isreplaced by acyl groups, as listed below, by using substituted hydrazineinstead of hydrazine and/or substituted biguanides instead ofdicyandiamide and/or by mono-acylating the guanazole with an acid beforethe acylation with the acrylic acid.

The amides of acrylic or methacrylic acid and diamino-l,2,4-triazolesare represented by the general formula:

CH2=CR co-on'n's in which R is hydrogen or the methyl group; G is adiamino-1,2,4-triazole group (guanazole nucleus); R' is the radical R",or an acyl group; and R is hydrogen or an alkyl, aryl, aralkyl, andalkaryl, or cycloaliphatic group. The diamino-1,2,4-triazole group whichis the pentavalent guanazole nucleus obtained by removing the fivehydrogen atoms from guanazole, has the following formula:

1i i t N One of these valences is satisfied by the acryl or methacrylgroup and the others by the R and R" groups as defined above. Thus inthe amides of this invention one or more of the hydrogen atoms ofguanazole other than that replaced by said acryl or methacryl group canbe replaced by such groups as methyl, ethyl, isopropyl, n-butyl,sec-butyl, amyl, hexyl, decyl, phenyl, tolyl, Xylyl, benzyl, phenethyl,naphthyl, cyclohexyl, cyclopentyl, and the like and one of thesehydrogen atoms can be replaced by an acyl group such as acryl,methacryl, acetyl, formyl, propionyl, butyryl, benzoyl, etc.Advantageously, the hydrocarbon substituents should contain not morethan a total of four carbon atoms and preferably should not contain morethan two carbon atoms each. The acyl substituents preferably are theacyl groups of the invention.

3 saturated mono-carboxylic acids (alkanoyl) preferably the for-myl andacetyl groups.

As an illustration the acrylic and methacrylic amides of guanazoleitself and their polymer units can be repwherein R is hydrogen ormethyl.

The proportions of the amide in the polymerization products of theinvention may vary over a wide range,

that is, from all or substantially all amide down to very small amountsof amide such as may be employed in acrylonitrile polymers to impart dyesusceptibility thereto. Although even smaller amounts are somewhatefiective,

V the improvement in susceptibility of acrylonitrile copolymers to dyesbecomes particularly noticeable when the amide content of the copolymeris at least about 0.1 percent and increases as the amount of amide isincreased.

Ordinarily sufiicient improvement in dye susceptibility is obtained withamounts of amide ranging up to about or percent but it may beadvantageous for reasons such as in the preparation of ion exchangepolymers or 1 additives to improve dyeing properties to have a majorproportion of amide in the acrylonitrile copolymer. In such cases theconcentration of amide may range up to or approaching 100 percent.Within these proportions acrylonitrile copolymers of the invention showgreat aflEinity toward many dyes especially acidic, vat, and celluloseacetate dyes.

In addition to the'improvements efiected in the resulting' copolymers,the use of amides of acrylic or methacrylic acid anddiamino-l,2,4-triazoles has certain other advantages over the use of theacids. For example, the amides are more soluble in acrylonitrile thanthe acids. Therefore, it is generally easier to get completecopolymerization of the amide with acrylonitrile in solution, emulsionand suspension polymerizations.

The acrylonitrile copolymers discussed herein are soluil ble inN,N-dimethyl acetamide (DMA), N,Ndimethyl formamide' (DMF),butyrolactone, ethylene carbonate, N,N-dimethyl methyl urethane of theformula (CH NCOOCH ethylene carbamate, N-methyl-2-pyrrolidone, and anumber of similar solvents, used alone or in conjunction withN,N-dimethyl cyanamide, N,N-dimethyl cyano-acetamide,

N,N-dimethyl methoxy-acetamide, methylene dinitrile, methylenedithiocyanate, formyl caprolactam, formyl morpholine, tetramethylenesulfone, etc. Nitroalkanes, such as nitromethane, may be used assolvents for such copolymers having no more than about 85 percentacrylonitrile, providing the comonomers used in preparing suchcopolymers do not have substituent groups of equal or greater secondarybonding force than the cyano groups of acrylonitrile. Copolymers of thepresent invention which have high proportions of monomers of relativelylow secondary-valence bonding strength, such as vinyl chloride, mayoften be dissolved in acetone or mixtures of acetone and solvents of theabove types.

. This invention will be more fully described 'by the following exampleswhich illustrate methods of practicing In these examples and throughoutthe specification, parts and percentages are intended to mean parts byweightand percentages by weight.

4 Example I 20.2 grams (0.2 mol) guanazole is admixed with approximately150 ml. diethyl ether and there is added slowly and with stirring 19.5grams (0.2 mol) acryl chloride. The mixture is refluxed forapproximately /2 hour, cooled, and the ether evaporated. The residue 'isdissolved in water and shaken with 29 grams (0.125 mol) silver oxide toremove the chloride ion. The mixture is filtered and the filtrateevaporated to dryness. The residue is recrystallized from absoluteethanol. There is obtained mono-acryl guanazolide.

Ultimate analysis for carbon, hydrogen and nitrogen and molecular weightdeterminations on the product give results which are in close agreementwith the theoretical values for mono-acryl guanazolide.

Substitution of equivalent quantities of methacryl chloride and thevarious diamino-1,2,4-triazoles, as described above, respectively, inthe foregoing procedure for the acryl chloride and guanazole there usedyields the various mono-acryl and methacryl guanazolides ofthe presentinvention.

Example 11 31.2 grams (0.2 mol) mono-acryl guanazolide (prepared as inExample I) is admixed with approximately 150 ml. diethyl ether and thereis added slowly and with stirring 19.5 grams (0.2 mol) acryl chloride.The mixture is refluxed for approximately /2 hour, cooled, and the etherevaporated. The residue is dissolved in water and shaken with 29 grams(0.125 mol) silver oxide to remove the chloride ion. filtrate evaporatedto'dryness. The residue is recrystallized from absolute ethanol. Thereis obtained di-acryl guanazolide.

Ultimate analyses for carbon, hydrogen and nitrogen and molecular weightdeterminations on the product give results which are in closeagreementwith the theoretical Example III Five polymers of acrylonitrile areprepared from the following monomer compositions:

Acrylo- Mono-acryl Polymer nitrile, guanazoparts lide, parts A- 100 0.0B 99. 9 0. l .0- 95 5.0 D 90 10. 0 E- 20. 0

To 900 parts of water, adjusted to a .pH of about three, in a suitablereactor, is added 1.0 part of am.- monium persulfate, 0.5 parts ofsodium bisulfite,'100 parts of monomer or comonomer mixture is added.The reactoris then flushed with deoxygenated nitrogen and heated withagitation to 50 C. for 24 hours. Steam is introduced into the reactor toremove unpolymerized monomer from the mixture. A small amount ofaluminum sulfate is added to the mixture and the polymer isolated byfiltration.

The polymer is then washed with water and with methyl alcohol. A portionof the polymer is dissolved in dimethyl formamide, in ethylenecarbonate, and in butyrolactone and a film cast from each solution. Thefilm is washed entirely free of solvent and stretched at a ratio ofabout 8:1 in a glycerine bath containing for each part of film 005 partof 1,5-diamino-4,8-dihydroxy-anthraquinone-3-sulfonic acid, 0.03 partsulfuric acid and The mixture is filtered and the.

essence 50 parts water (50:1 bath-film) ratio at boiling temperature forone hour. The film is then removed and washed with water and scoured forminutes in a 0.4 percent soap solution at 85 C. Whereas the unmodifiedpolyacrylonitrile treated in this manner had little or no color, all ofthe copolymers were dyed to a deep blue shade.

Fibers are spun from the same solutions either by dry spinning or by wetspinning. The fibers are substantially freed from solvent and dried.After cold-drawing the dried fibers 600-900 percent at 120145 C. andsubsequently heat-treating them at 150 C. for one hour, the fibers aregiven the same dyeing and washing treatment described above with thesame results as for the films, a light tint being acquired by theunmodified polyacrylonitrile fibers and a deep and dense color beinggiven to the copolymer fibers. The polymers of this example are alsosoluble in dimethyl formamide, dimethyl acetamide, butyrolactone,forrnyl morpholine, etc.

Example IV Five parts of the copolymer fiber C of Example III is dyed toa green shade using the vat color, dimethoxydi-benzanthrone, at 70 C. ina bath containing 0.5 part of dye, 0.2 part sodium hydroxide, 0.5 partsodium hydrosulfite and 100 parts of water (:1 bath-fiber ratio). Afterthe first 15 minutes of heating, 0.25 part of Glaubers salt is added.The fiber sample is then oxidized in a 0.5 percent sodium dichromate 1.0percent acetic acid aqueous solution at 70 C. for minutes in a 20:1bath-fiber ratio. The dyed fiber is then scoured in a 0.5 percentboiling soap solution. A sample of yarn prepared from the unmodifiedacrylonitrile polymers and dyed under the same conditions acquired onlya light shade of color.

When l,5-di-p-anisoylamino 4,8 dihydroxyanthraquinone is used as the vatdye, the fiber is dyed a strong violet color.

The procedure of this example and of Example III can be used with thevarious other amides of acrylic or methacrylic acid anddiamino-l,2,4-triazole described above instead of the mono-acrylguanazolide.

Example V The procedure of Example III is repeated for thepolymerization of the following monomer compositions:

Sometimes copolymers D and E, when dissolved in nitrornethane may havegelled, partially dissolved particles known as fisheyes. In such cases,the solubility can be improved by the addition of small amounts ofmaterials which are good solvents for acrylonitrile polymers, such asbutyrolactone, ethylene carbonate, dimethyl formamide, dimethylacetamide, tetramethyl urea, etc. In addition, certain materials whichare relatively poor solvents for polyacrylonitrile, such as diethylformarnide, diethyl acetarnide, diethyl propionamide, etc., can be addedto improve the solubility. Also, when acetone solutions of copolymer Fcontain gelled particles, clarification of the solution may be effectedby the addition of nitromethane, diethyl formamide, diethyl acetamide,etc.

Dyeing tests of these copolymers show improvements in dyeingsusceptibility similar to those of Example III.

Instead of mono-acryl guanazolide there may be used the various otheramides of acrylic or methacrylic acid and diamino-1,2,4-triazolesdescribed above.

Example VI The procedure of Example III is repeated for thepolymerization of the following monomer compositions:

Mono- Acrylo- Styrene, acryl Polymer nitrile, parts guanaparts zolide,

parts Dyeing tests of these copolymers show improvements in dyesusceptibility similar to Example III. In place of styrene, variousstyrene derivatives can be used, such as alpha-methyl-styrene;nuclear-substituted chloro-styrenes, i. e., ortho-, meta-, andpara-chloro-styrenes, dichlorostyrenes, for example, the 2,3-, 2,4-,2,5-, 2,6-, 3,4-, and 3,5-dichloro-styrenes, trichloro-styrenes;cyano-styrenes, such as ortho-, meta-, and para-cyano-styrenes,dicyano-styrenes; nuclear-substituted alkyl-styrenes, such as monoanddi-methyl'styrenes, monoand diethylstyrenes, monoanddi-isopropyl-styrenes; aryl-substituted styrenes, i. e.,para-phenyl-styrene, etc., cycloaliphaticsubstituted styrenes, such aspara-cyclohexyl-styrene; fluoro-styrenes such as ortho-, meta-,para-fluoro-styrene, difluoro-styrenes, etc.; trifiuoro-methyl-styrenes,such as ortho-, meta-, and para-trifluoromethyl-styrenes,di(trifiuoromethyD-styrenes, and various other styrenes or mixtures ofany number of these with each other or with styrene.

Instead of mono-acryl guanazolide there can be used the various otheramides of acrylic or methacrylic acid and diamino-1,2,4-triazolesdescribed above.

Example VII The procedure of Example III is repeated for thepolymerization of the following monomer compositions:

Vinyli- Mono- Acrylodene methacryl Copolymer soluble Polymer nitrile,chloride, guanazoinparts parts lide,

parts 85 5 10 DMF, DMA, etc.

65 25 10 DMF, DMA, etc,

45 45 10 DMF, DMA, etc.

25 65 10 DMF, DMA, etc.

5 85 1O DMF, DlVIA, etc.

With the above vinylidene chloride copolymers and similar copolymershaving a total of acrylonitrile and vinylidene chloride of at least 85percent in the polymer molecules, only the same active solvents, such asbutyrolactone, ethylene carbonate, N,N-dimethyl acetamide, N,N-dimethylformamide, etc., can be used as solvents. The above copolymers dyereadily and thoroughly than similar copolymers containing noguanazolide.

Example VIII The procedure of Example III is repeated for thepolymerization of the following monomer compositions:

Mono- Acrylo- Vinyli- Vinyl amide of Polymer nitrile, dene chloride,guanaz le parts chloride, parts and acryL parts ic acid,

parts The dyeing tests of the copolymer products show dye susceptibilitysimilar to the copolymers of Example III.

Instead of mono-acryl guanazolide there can be used the various otheramides of acrylic or methacrylic acid and diamino-1,2,4-triazolesdescribed above.

Instead of copolymerizing the amides of this invention withacrylonitrile, they may be polymerized independently to producepolymeric amides of acrylic or methacrylic acid anddiamino-1,2,4-triazoles and the prepared homopolymer used to modifypolyacrylonitrile or acrylonitrile copolymers. The acrylonitrilepolymers may be blended with up to 10 percent or more of thehomo-polymer without serious loss in the physical or chemical propertiesof the resulting dyed structures. The following example is illustrative.

Example IX Polymeric mono-acryl guanazolide is prepared substantially inaccordance with the procedure of Example III. A 10 percent solution ofthis homo-polymer is prepared in dimethyl formamide and added to adimethyl formamide solution of polyacrylonitrile containing percentpolymer so that a composition containing 90 parts of polyacrylonitrileand 10 parts of the polymeric monoacryl guanazolide is obtained. Thesolution is heated to 130 C. after which the solution is filtered. Filmsand fibers prepared from this mixture are dyed in accordance with theprocess of Example III and satisfactory, dyed, shaped articles areobtained. The unmodified polyacrylonitrile without the addition of thepolymeric mono-acryl guanazolide shows little or no dye retention.

Instead of using a homopolymer of the mono-acryl guanazolide copolymerssuch as polymers D and E of Example III can be used as modifiers fortheunmodified homopolymers of acrylonitrile. For example, polymer E ofExampleIlI which consists of 80 parts of acrylonitrile and 20 parts ofthe mono-acryl guanazolide has excellent compatibility with homopolymersof acrylonitrile and has less detrimental effect on the physicalproperties of the oriented fibers and films. In many cases it isdesirable to use amide-acrylonitrile copolymers which have even a higherratio of the amide as, for example, 50 to 70 parts of the amidecopolymerized with acrylonitrile or methacrylonitrile. In other casesthe copolymers of amide with other monomers are satisfactory such as,for example, copolymers of styrene, vinyl chloride, vinylidene chloride,alpha-methyl-styrene, etc.

When it is desired to modify an acrylonitrile copolymer such as thecopolymer of acrylonitrile and styrene or the copolymers ofacrylonitrile and other copolymerizable ethylenic compounds, it isusually desirable to use as modifiers copolymers containing at least onestructural unit present in the acrylonitrile copolymer. Thus as thereare present in the acrylonitrile copolymer, structural units derivedfrom the acrylonitrile and styrene, it is desirable to have present inthe modifying copolymer structural units derived from styrene and/oracrylonitrile, advantageously both, in addition to those derived fromthe amide. By thus including in the modifying copolymers structuralunits of the same type as the structural units of the copolymer to bemodified, greater compatibility between the acrylonitrile copolymer tobe modified and the modifying copolymer is obtained and the two are morereadily soluble in the mutual solvent and Will more readily mix intohomogeneous polymer mixtures.

The polymerization products of the present invention have in the polymermolecule a plurality of repeating units of the formula -CH2(|3R C0-GRR;v

in Which R, R, R, and G are as indicated above and when the amide iscopolymerized with acrylonitrile will contain additional repeating unitsof the formula oHloH In addition, the polymerization products cancontain acid and a diamino-1,2,4-triazole or a mixture of acrylonitrileand the amide with one or more copolymerizable ethylenic compounds, suchas, for example, vinylidene chloride, vinyl chloride, styrene,alpha-methyl-styrene, methacrylonitrile, fumaronitrile,beta-cyano-acrylamide and methyl beta-cyano-acrylate.

As previously indicated, the solvent resistance of copolymers thatcontain one or more monomer units in addition to those formed by theacrylonitrile and the amides of the invention is affected by the typeand proportion of copolymerizing monomer'or monomers used to replacepart of the acrylonitrile. For example, copolymers containing smallamounts of the amide units can contain various proportions of suchmonomer units as obtained from vinylidene chloride, methacrylonitrile,fumaronitrile, and beta-cyano-acrylamide without considerable reductionin solvent resistance.

Replacement of acrylonitrile units in the copolymers by vinyl chloride,styrene andalpha-methyl-styrene units results in copolymers of loweredsolvent resistance, the amount of such lowering in resistance in eachcase depending on the amount substituted. In addition to the solventresistance, certain other physical properties of the copolymers areaifected by the presence of these additional units in the copolymers.The amount and character of the changes in physical properties of thesecopolymers depend again on the type and proportion of copolymerizingmonomer or monomers used. For example, the tensile strength of anacrylonitrile-amide type copolymer will decrease-much more when one ormore monomers having relatively weak secondary bonding forces, such asstyrene or ethylene is used to replace part ofv the acrylonitrile than,when one or more monomers having relatively strong bonding forces, suchas methacrylonitrile, fumaronitrile, beta-cyano-acrylamide, methylbetacyano-acrylate and vinylidene chloride, is used to replace part ofthe acrylonitrile. Moreover, the ability of these copolymers to formmolecularly oriented shaped articles depends on the type and amount ofthe copolymerizing monomer or monomers used to replace acrylonitrile.

Other copolymerizable ethylenic compounds, which can also be present inthe polymerizable masses for copolymerization with amides of acrylic ormethacrylic acid and diamino-1,2,4-triazoles, with or withoutacrylonitrile, in-

clude one or more of the following: acrylates, e. g. methyl acrylate;methacrylates, e. g. methyl methacrylate; acrylamides; methacrylamides;vinyl esters, such as vinyl acetate; maleates, such as dimethyl anddiethyl maleates; fumarates, such as dimethyl and diethyl fumarates;itaconic diesters, such as dimethyl and diethyl itaconates; itaconamide;vinyl halides, such as vinyl fluoride, vinylidene fluoride,tetrafluoroethylene, trifluorochloroethylene; vinyl aryls, such as vinylnaphthalenes and substituted styrenes as listed in Example VI, etc.

The polymerization products of this invention can be prepared by variouspolymerization systems, such as emulsion, suspension, mass and solutionpolymerizations. In addition to the monomers, the polymerizable mass mayalso contain other materials such as catalysts, e. g. peroxides, such asbenzoyl peroxide, naphthyl peroxides, phthalyl peroxide, tertiary-butylhydro-peroxide, hydrogen peroxide, cyclohexyl hydro-peroxide,tertiary-butyl perbenzoate, etc., azo catalysts, persulfates, such asammonium persulfate, etc., solvents, suspension or emulsion media,emulsifying agents, suspension agents, plasticizers, lubricants, etc.

For use in the preparation of shaped articles, the polymerizationproducts of this invention have molecular weights preferably of at leastabout 10,000. However, polymerization products of molecular weights lessthan 10,000 may be used for other purposes, such as impregnants, solventresistant coatings, etc. The molecular weight of the polymerizationproducts is dependent on the concentrations of the monomers, the amountand type of catalyst, the temperature of reaction, etc.

As is quite generally known in the field of high polymers, molecularorientation is usually indicated and identified by birefringence orpolarized light, as under Nicol prisms, by increased density as comparedto the density of the same polymer unoriented, and by characteristicX-ray dilfraction patterns. When a material is crystalline or oriented,its X-ray diagram shows bright areas or spots for points ofcrystallization and dark areas for the noncrystalline regions. Theintensity or number of these bright spots increases with the degree oforientation or crystallization. Amorphous or non-crystalline materialsgive X-ray diagrams having very few high lights or bright spots whereascrystalline or oriented materials give definite X-ray diffractionpatterns. In these patterns there are definite relationships of thebright spots with regard to position and spacing which are generallycharacteristic of the composition of the material being X-rayed. Infibers or films the orientation usually follows the direction of drawingor stretching so that the orientation is parallel to the fiber axis or amajor surface.

Useful fibers can be made from the solutions of the copolymers of thisinvention by dry spinning, as in the preparation of cellulose acetatefibers, or by wet spinning, as in the preparation of viscose rayon. InWet spinning, the solution of copolymer can be spun into a substancewhich is a non-solvent for the copolymer, but which is advantageouslycompatible with the solvent in which the copolymer is dissolved. Forexample, Water, acetone, methyl alcohol, carbon disulfide, glycerine,chloroform, carbon tetrachloride, benzene, etc., may be used as aprecipitating bath for N,N-dimethyl acetamide, N,N,N',N'- tetramethylurea, butyrolactone, ethylene carbonate, and other solvent compositionsof these copolymers. The extruded fibers, from which substantially allof the solvent has been removed in the spinning Step, about 1-10 percentremaining in the shaped article, can.then be colddrawn about 100-900percent, preferably about 300600 percent; and the drawn fiberheat-treated, usually at substantially constant length, at about 100-160C. to eifect further crystallization and removal of the remainingsolvent. The term heat-treated, as used herein, refers to theapplication of heat to an object, usually at a controlled temperatureand usually by means of the medium surrounding the object.

Many of the acrylonitrile copolymers of this invention can bemolecularly oriented, especially if there is no more than 15 percent ofamide in the copolymer molecule. This is true when the major portion ofthe copolymer is acrylonitrile, for example, 85 percent or moreacrylonitrile, or when the other copolymerizing monomers used in makingsuch copolymers have substituent groups having secondary-valence bondingforces equal to or greater than exhibited by the cyano group inacrylonitrile. For example, if such monomers as methacrylonitrile,fumaronitrile, vinylidene chloride, beta-cyano-acrylamide and methylbeta-cyano-acrylate are used with acrylonitrile and an amide accordingto the invention, the proportion of acrylonitrile in the copolymers canbe much less than 85 percent without destroying the capacity formolecular orientation. Molecularly oriented, cold-drawn, shaped articlesof particular usefulness are prepared from copolymer compositionscontaining in the polymer molecules 60-999 percent acrylonitrile, 0.1l5percent advantageously 0.1-5 percent the amide, with or without one ormore monomers of the class consisting of vinylidene chloride, vinylchloride, styrene, alpha-methyl-styrene, methacrylonitrile,fumaronitrile, beta-cyano-acrylamide and methyl beta-cyano-acrylate, theeffects of the presence of the monomers of this class being noticeablewhen the monomer is present in the polymer molecule in amounts of onepercent or more.

The polymerization products of this invention show great afiinity forthe acetate, acidic and vat dyes. The

cellulose acetate dyes which are effective with these polymerizationproducts are mainly amino anthraquinone derivatives. A number of otheracidic dyes that can be used are anthranilic acidl-(4-sulfophenyl)-3-methyl- 5-pyrazolone; 1,5-diamino-4,8-clihydroxyanthraquinone- 3-sulfonic acid; l-amino-naphthalene-4-sulfonicacidalpha-naphthol-4-sulfonic acid; the sodium salt of sulfanilic acid-aaniline Z-benzoyl amino-5-naphthol-7sulfonic acid; the sodium salt of4,4'-diamino-stilbene-2,2'-di-su1- fonic acid (phenol) 2 ethylated;1,5-diamino-4,8-dihydroxy-anthraquinone-3-sulfonic acid; dye prepared bydiazotizing 1-amino-naphthalene-4-sulfonic acid and coupled withalpha-naphthol-4-sulfonic acid; the sodium salt of (m-aInino-benzoicacido-anisidine) phosgenated; the sodium salt of(2-naphthol-6,8-disulfonic acid -benzidine ephenol) ethylated;dimethoxy-dibenzanthrone; and 1,5-di-p-anisoylamino-4,8-dihydroxy-anthraquinone.

From the molecularly orientable copolymers of this invention fibers canbe prepared having improved dyeing properties, low shrinkage in boilingwater, sometimes as low 3 to 5 percent or less of the cold-drawn orstretched article, good heat resistance, and tensile strength in theorder of 4 to 6 grams per denier. Moreover, these properties make thefibers desirable in the manufacture of hosiery and for such all-purposefabrics as used for blouses, shirts, suits, etc.

This application is a continuation of my presently copending applicationSerial No. 244,697, filed August 31, 1951 now abandoned.

What is claimed is:

1. As a new monomeric composition, the mono-amide of guanazole andacrylic acid.

2. As a new monomeric composition the mono-amide of guanazole andmethacrylic acid.

3. A homopolymeric composition of the monomeric composition of claim 1.

4. As a new monomeric composition a member selected from the groupconsisting of mono-amide of diamino-1,2,4-triazole and acrylic acid andthe mono-amide of diamino-1,2,4-triazole and methacrylic acid.

5. A homopolymeric composition of the monomeric composition of claim 4.

6. A copolymer of a polymerizable amide as defined in claim 1 and apolymerizable monomer having a group.

7. A copolymer of a mono-amide selected from the group consisting of themono-amide of guanazole and acrylic acid and guanazole and methacrylicacid and a polymerizable monomer selected from the group consisting ofacrylonitrile, vinyl chloride, vinylidene chloride, styrene,alpha-methyl-styrene, methacrylonitrile, fumart nitrile,beta-cyano-acrylamide, and methyl beta-cyanoacrylate.

8. A cold-drawn shaped article having molecular orientation and dyesusceptibility to acid dyes, said article comprising a copolymer ofacrylonitrile and an amide as defined in claim 1.

9. A cold-drawn fiber having molecular orientation and dyesusceptibility to acid dyes, said fiber comprising a copolymer ofacrylonitrile and the mono-amide of guanazole and acrylic acid, saidcopolymer having a molecular weight of at least about 10,000 andcontaining in the polymer molecule no more than about 15 percent byweight of said amide.

10. A cold-drawn fiber having molecular orientation and dyesusceptibility to acid dyes, said fiber comprising a copolymer of about60-989 percent by weight acrylonitrile, about 0.1 to 5 percent by weightof a member selected from the group consisting of the mono-amide ofguanazole and acrylic acid and the mono-amide of guanazole andmethacrylic acid, and about 1 to 39.9 percent by weight of a compoundselected from the class consisting of vinyl chloride, vinylidenechloride, styrene,

11 7 alphamethyl-styrene, methacrylonitrile, fumaronitrile,beta-cyano-acrylamide, and methyl beta-cyano-acrylate.

11. A cold-drawn fiber having molecular orientation and dyesusceptibility to acid dyes, said fiber comprising a copolymer of about60-989 percent by weight acrylonitrile, about 0.1 to percent by weightof a member selected from the group consisting of the mono-amide ofguanazole and acrylic acid and the mono-amide of guanazole andmethacrylic acid, and about 1 to 39.9 percent by weight vinylidenechloride.

12. A cold-drawn fiber having molecular orientation and dyesusceptibility to acid dyes, said fiber comprising a copolymer of about60-989 percent by weight acrylonitrile, about 0.1 to 5 percent by weightof a member selected from the group consisting of the mono-amide ofguanazole and acrylic acid and the mono-arnide of guanazole andmethacrylic acid, and about 1 to 39.9 percent by weight vinyl chloride,

13. A cold-drawn fiber having molecular orientation and dyesusceptibility to acid dyes, said fiber comprising a copolymer of about60-983 percent by weight acrylonitrile, about 0.1 to 5 percent by weightof a member selected from the group consisting of the mono-amide 12ofguanazoleand acrylic acid and the mono-amide of guanazole andmethacrylic acid, and about 1 to 39.9 per,- cent by weight styrene. 4

14. A cold-drawn fiber having molecular orientation and dyesusceptibility to acid dyes, said fiber comprising a copolymer of about-989 percent by weight acrylonitrile, about 0.1 to 5 percent by weightanamide as defined in claim 1.

15. A cold-drawn shaped article having molecular orientation and dyesusceptibility to acid dyes, said article comprising a copolymer ofabout 6098.9 percent by weight acrylonitrile, about 0.1 to 5 percent byweight of an amide as defined in claim 1.

References Cited in the file of this patent UNITED STATES PATENTS 12,320,850 DAlelio June 1, 1943 2,395,776 Bavley Feb. 26, 1946 2,567,836Anthes Sept. 11, 1951 FOREIGN PATENTS 468,044 Canada Sept. 12, 1950

10. A COLD-DRAWN FIBER HAVING MOLECULAR ORIENTATION AND DYESUSCEPTIBILITY TO ACID DYES, SAID FIBER COMPRISING A COPOLYMER OF ABOUT60-98.9 PECENT BY WEIGHT ACRYLONITRILE, ABOUT 0.1 TO 5 PERCENT BY WEIGHTOF A MEMBER SELECTED FROM THE GROUP CONSISTING OF THE MONO-AMIDE OFGUANAZOLE AND ACRYLIC ACID AND THE MONO-AMIDE OF GUANAZOLE ANDMETHACRYLIC ACID, AND ABOUT 1 TO 39.9 PERCENT BY WEIGHT OF A COMPOUNDSELECTED FROM THE CLASS CONSISTING OF VINYL CHLORIDE, VINYLIDENECHLORIDE, STYENE, ALPHA - METHYL - STYRENE, METHACRYLONITRILE,FUMARONITRILE, BETA-CYANO-ACRYLAMIDE, AND METHYL BETA-CYANO-ACRYLATE.